Molecular Response Functions for the Polarizable Continuum Model

Cammi, Roberto

doi:10.1007/978-3-319-00987-2

Cited by 32 publications

(34 citation statements)

References 46 publications

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“…The operator

{\overset{V}{true}}_{normale} (Ψ)

is represented in terms of a set of polarization point charges located at the cavity surface, and it may be written as:

{\overset{V}{true}}_{normale} (Ψ) = \overset{true¯}{boldQ} (Ψ) \cdot \overset{truê}{boldV}

where

\overset{true¯}{boldQ} (Ψ)

is a vector collecting the set of polarization charges induced by the charge distribution of the solute,

\overset{truê}{boldV}

is a vector operator representing the electrostatic potential of the solute at the boundary of the cavity, and the dot represents an inner product. The argument of the polarization charge

\overset{true¯}{boldQ} (Ψ)

denotes its nonlinear character as a results of its dependence on the electronic wave‐function

Ψ

of the molecular solute…”

Section: Basic Formulation Of the Methodsmentioning

confidence: 99%

“…QðWÞ ÁV1V r jW > 1Ṽ nn (6) whereṼ nn is the nuclei-nuclei interaction contribution in the presence of the external medium. Within the onedeterminantal description of the electronic wave-function of the solute, with a basis set expansion of the molecular orbitals (MO), the free-energy functional G e2r can be written in the following form…”

Section: The Free-energy Functional G Ermentioning

confidence: 99%

“…This article is part of a systematic investigation toward the development of a Quantum Chemical method for the description of molecular processes and properties at extreme high pressures, of the order of GPa (

1 GPa = 10^{4} bar

). The method, denoted with the acronym PCM‐XP (i.e., PCM for eXtreme Pressure), is based on an extension of the Polarizable Continuum Model (PCM) originally developed for the study of molecules in solution at the standard conditions of pressure (

p = 1 bar = 10^{- 4} GPa

) and temperature.…”

Section: Introductionmentioning

confidence: 99%

“… The solvent polarization charges

\overset{true¯}{boldQ} (Ψ)

depend on the wave‐function of the solute as expectation value

\overset{true¯}{boldQ} (Ψ) = < Ψ | \overset{truê}{boldQ} | Ψ >

of a suitable apparent charge operator

\overset{truê}{boldQ}

. There are several definitions of the

\overset{truê}{boldQ}

operator according to the several variants of the PCM method . Here, we refer to the Integral Equation Formalism version (IEF‐PCM) …”

mentioning

confidence: 99%

See 3 more Smart Citations

A new extension of the polarizable continuum model: Toward a quantum chemical description of chemical reactions at extreme high pressure

Cammi

2015

J Comput Chem

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123

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A quantum chemical method for studying potential energy surfaces of reactive molecular systems at extreme high pressures is presented. The method is an extension of the standard Polarizable Continuum Model that is usually used for Quantum Chemical study of chemical reactions at a standard condition of pressure. The physical basis of the method and the corresponding computational protocol are described in necessary detail, and an application of the method to the dimerization of cyclopentadiene (up to 20 GPa) is reported.

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“…The operator

{\overset{V}{true}}_{normale} (Ψ)

is represented in terms of a set of polarization point charges located at the cavity surface, and it may be written as:

{\overset{V}{true}}_{normale} (Ψ) = \overset{true¯}{boldQ} (Ψ) \cdot \overset{truê}{boldV}

where

\overset{true¯}{boldQ} (Ψ)

is a vector collecting the set of polarization charges induced by the charge distribution of the solute,

\overset{truê}{boldV}

is a vector operator representing the electrostatic potential of the solute at the boundary of the cavity, and the dot represents an inner product. The argument of the polarization charge

\overset{true¯}{boldQ} (Ψ)

denotes its nonlinear character as a results of its dependence on the electronic wave‐function

Ψ

of the molecular solute…”

Section: Basic Formulation Of the Methodsmentioning

confidence: 99%

Section: The Free-energy Functional G Ermentioning

confidence: 99%

1 GPa = 10^{4} bar

p = 1 bar = 10^{- 4} GPa

) and temperature.…”

Section: Introductionmentioning

confidence: 99%

“… The solvent polarization charges

\overset{true¯}{boldQ} (Ψ)

depend on the wave‐function of the solute as expectation value

\overset{true¯}{boldQ} (Ψ) = < Ψ | \overset{truê}{boldQ} | Ψ >

of a suitable apparent charge operator

\overset{truê}{boldQ}

. There are several definitions of the

\overset{truê}{boldQ}

operator according to the several variants of the PCM method . Here, we refer to the Integral Equation Formalism version (IEF‐PCM) …”

mentioning

confidence: 99%

See 2 more Smart Citations

A new extension of the polarizable continuum model: Toward a quantum chemical description of chemical reactions at extreme high pressure

Cammi

2015

J Comput Chem

Self Cite

123

View full text Add to dashboard Cite

show abstract

“…These methods typically define a solute cavity to be composed of atom-centered spheres based on van der Waals radii, although other cavity definitions are used as well to better approximate the molecular shape. Among the most popular of these methods is the celebrated polarizable continuum model (PCM), 20,21,23,24 which has been applied successfully to compute a variety of molecular properties. 20 Another method in the ASC family which has been widely used is the conductor-like screening model (COSMO).…”

Section: Introductionmentioning

confidence: 99%

Electronically Excited States in Solution via a Smooth Dielectric Model Combined with Equation-of-Motion Coupled Cluster Theory

Howard

Womack

Dziedzic

et al. 2017

J. Chem. Theory Comput.

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We present a method for computing excitation energies for molecules in solvent, based on the combination of a minimal parameter implicit solvent model and the equation-of-motion coupled-cluster singles and doubles method (EOM-CCSD). In this method, the solvent medium is represented by a smoothly varying dielectric function, constructed directly from the quantum mechanical electronic density using only two tunable parameters. The solvent-solute electrostatic interactions are computed by numerical solution of the nonhomogeneous Poisson equation and incorporated at the Hartree-Fock stage of the EOM-CCSD calculation by modification of the electrostatic potential. We demonstrate the method by computing excited state transition energies and solvent shifts for several small molecules in water. Results are presented for solvated HO, formaldehyde, acetone, and trans-acrolein, which have low-lying n → π* transitions and associated blue shifts in aqueous solution. Comparisons are made with experimental data and other theoretical approaches, including popular implicit solvation models and QM/MM methods. We find that our approach provides surprisingly good agreement with both experiment and the other models, despite its comparative simplicity. This approach only requires modification of the Fock operator and total energy expressions at the Hartree-Fock level-solvation effects enter into the EOM-CCSD calculation only through the Hartree-Fock orbitals. Our model provides a theoretically and computationally simple route for accurate simulations of excited state spectra of molecules in solution, paving the way for studies of larger and more complex molecules.

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Analytical calculation of pressure for confined atomic and molecular systems using the eXtreme‐Pressure Polarizable Continuum Model

2018

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We show that the pressure acting on atoms and molecular systems within the compression cavity of the eXtreme-Pressure Polarizable Continuum method can be expressed in terms of the electron density of the systems and of the Paulirepulsion confining potential. The analytical expression holds for spherical cavities as well as for cavities constructed from van der Waals spheres of the constituting atoms of the molecular systems.

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Molecular Response Functions for the Polarizable Continuum Model

Cited by 32 publications

References 46 publications

A new extension of the polarizable continuum model: Toward a quantum chemical description of chemical reactions at extreme high pressure

A new extension of the polarizable continuum model: Toward a quantum chemical description of chemical reactions at extreme high pressure

Electronically Excited States in Solution via a Smooth Dielectric Model Combined with Equation-of-Motion Coupled Cluster Theory

Analytical calculation of pressure for confined atomic and molecular systems using the eXtreme‐Pressure Polarizable Continuum Model

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